Process for breaking petroleum emulsions employing certain polyepoxide treated derivatives obtained by reaction of monoepoxides with resins



PROCESS FOR BREAKING PETROLEUM EMUL SIONS EMILOYING CERTAIN POLYEPOXIDE TREATED DERIVATIVES OBTAINED BY REAC- TION OF MONOEPOXIDES WITH lRElN Melvin De Groote, University City, and KWan-Ting Sheri, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Application June 10, 1953,

Serial No. 360,842

20 Claims. Cl. 252-344 The present invention is a continuation-in-part of our cc-pending application, Serial No. 350,532, filed April 22, 1953, now Patent No. 2,771,431 dated November 20, 1956.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil .type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the invention.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

The present invention is concerned with the breaking of emulsions of the water-in-oil-type by subjecting them to the action of products obtained by a 3-step manufacturing process involving (1) condensing certain phenol aldehyde resins, hereinafter described in detail, with certain basic hydroxylated secondary monoamines, hereinafter described in detail, and formaldehyde; (2) oxyalkylation of the condensation product with certain monoepoxides, hereinafter described in detail; and (3) oxyalkylation of the previously oxyalkylated resin condensate with certain non-aryl hydrophile polyepoxides, also hereinafter described in detail.

The present invention is characterized by the use of compounds derived from diglycidyl ethers which do not introduce any hydrophobe properties in its usual meaning but in fact are more apt to introduce hydrophile properties. Thus, the diepoxides employed in the present invention are characterized by the fact that the divalent radical connecting the terminal epoxide radicals contains less than 5 carbon atoms in an uninterrupted chain.

The diepoxides employed in the present process are obtained from glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, diglycerol, triglycerol, and similar compounds. Such products are well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be nonaryl or aliphatic in character. The diglycidyl ethers of co-pending application, Serial No. 350,532, are invariably and inevitably aryl in character.

The diepoxides employed in the present process are usually obtained by reacting a glycol or equivalent compound, such as glycerol or diglycerol, with epichlorohydrin and subsequently with an alkali. Such diepoxides have been described in the literature and particularly the patent literature.

Reference to being thermoplastic characterizes products as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents such as alcohols, ketones, esters, ethers, mixed solvents, etc. to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it sometimes is desirable to dilute the compound containing the epoxy rings before reacting with an oxyalinstances, of course, the solvent selected would have to be one which kylated amine condensate. In such is not susceptible to oxyalkylation, as, for example, kero sene, benzene, toluene, dioxane, possibly various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethylene-glycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the Word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. course, 1,2-epoxy rings or oxirane rings in the alphaomega position. This is a departure from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as l,2-epoxy-3,4- epoxybutane(1,2,3,4 diepoxybutane).

It well may be that even though the previouslysu'ggested formula represents the principal component, or components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric compounds containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be H HH or if derived from cyclic diglycerol and structure would be thus:

Reference 7 They usually represent, of

. 3 or the equivalent compound wherein the ring structure involves only 6 atoms, thus:

Commercially available com-pounds seem to be largely the former With comparatively small amounts, in fact, comparatively minor amounts, of the latter.

Having obtained an acyclic reactant having generally 2 epoxy rings as depicted in the next to last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place With any oxyalkylated phenolaldehyde resin condensate by virtue of the fact that there are always present either phenolic hydroxyl radicals or alkanol radicals resulting from the oxyalkylation of the phenolic hydroxyl radicals; there may be present reactive hydrogen atoms attached to a nitrogen atom or an oxygen atom, depending on whether initially there was present a hydroxylated group attached toan amino hydro-gen group or a secondary amino group. In any event there is always a multiplicity of reactive hydrogenatoms present in the oxyalkylated amine-modified phenol-aldehyde resin.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having 2 oxirane rings and an oxyalkylated amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of 2 moles 'of the oxyalkylated amine condensate to one mole of theoxyalkylating agent gives a product which may be indicated as follows:

in which n is a small wholenumber less than 10, and usually less than 4, and including 0, and R1 represents a divalent radical as previously described being free from any radical having more than 4 uninterrupted carbon atoms in a single chain, and the characterization oxyalkylated condensate is simply an abbreviation for the condensate which is described in greater. detail subsequently.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other Words, the nitrogen groups present, Whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with Water) or a salt form such as the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from 4 V instances Where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their weight of 5% gluconic acid at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone. As oxyalkylation proceeds the significance of the basicity of any nitrogen group is obviously diminished.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufficiently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a Waterinsoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience, what is said hereinafter will be divided into seven parts:

Part 1 is concerned with the hydrophile nonaryl polyepoxides and'particularly diepoxides employed as reactants;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield an amine-modified resin;

Part 3 is concerned with appropriate basic hydroxylated secondary monoarnines which may be employed in the preparation resins;

Part 4 is concerned with reactionsinvolving the resin, the amine and formaldehyde to produce specific products of the herein-described amine-modified or compounds which are then subjected to oxyalkylation' .with monoepoxides;

Part 5 is concerned with the oxyalkylation of the products described in Part 4, preceding;

Part. 6 is concerned with reactions involving the two preceding types of materials and'examples obtained by such reactions. Generally speaking, this'involves nothing more than a reaction between two moles of a previouslyprepared oxyalkylated amine-modified phenol-aldehyde resin condensate as described and one mole of a polyepoxide so as to yield a newand larger resin molecule or comparable product;

I Part7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products.

PART 1 Reference is made to various patents as illustrated in the manufacture of the non-aryl polyepoxides and particularly diepoxides employed as reactants in the instant invention. More specifically, such patents are the following: Italian Patent No. 400,973, dated August 8, 1941; British Patent No. 518,057, dated December 10, 1938; U. S. Patent No. 2,070,990, dated February 16, 1937 to Groll et al.; and U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech. The simplest diepoxide is probably the one derived from 1,3-butadiene or isoprene. Such derivatives are obtained by the use of peroxides or by other suitable means and the diglycidyl ethers may be indicated thus:

In some instances the compounds are essentially derivatives of etherized epichlorohydrin or methyl epichlorohydrin. Needless to say, such compounds can be derived from glycerol monochlorohydriu by etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent No. 400,973:

Another type of diepoxide is diisobutenyl dioxide as described in aforementioned U. S. Patent No. 2,070,990, dated February 16, 1937, to Groll, and is of the following formula The diepoxides previously described may be indicated by the following formula:

n O in which R represents a hydrogen atom or methyl radical and R" represents the divalent radical uniting the two terminal epoxide groups, and n is the numeral 0 or 1. As previously pointed out, in the case of the butadiene derivative, n is 0. In the case of diisobutenyl dioxide R is CHz-CI-Iz and n is 1. In another example previously referred to R" is CHzOCHz and n is 1.

However, for practical purposes the only diepoxide available in quantities other than laboratory quantities is a derivative of glycerol or epichlorohydrin. ticular diepoxlde is obtained from diglycerol which is largely acyclic diglycerol, and epichlorohydrin or equivalent thereof in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycols or polyglycols and it is more convenient to include as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl epichlorohydrin. So presented the formula becomes:

In the above formula R1 is selected from groups such as the following:

CzHaOCzHs This par- I CaH-tOCaH4Oca H4 CsHe CaHeOCaI-Ie CsHeOCaHsOCaHe CaH5(OH) OCaH5(OH) Cal-I5 OH) OCaHs OCaHsOH) It is to be noted that in the above epoxides there is a complete absence of (a)-aryl radicals and (b) radicals in which 5 or more carbon atoms are united in a single uninterrupted single group. R1 is inherently hydrophile in character as indicated by the fact that it is specified that the precursory diol or polyol HOROH must be watersoluble in substantially all proportions, i. e., water miscible.

Stated another way, what is said previously means that a polyepoxide such as is derived actually or theoretically, or at least derivable, from the diol HOROH, in which the oxygen-linked hydrogen atoms were replaced by Thus, R(OH)n, where n represents a small whole number which is 2 or more, must be water-soluble. Such limitation excludes polyepoxides if actually derived or theoretically derived at least, from water-insoluble diols or water-insoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms or thereabouts.

Referring to a compound of the type above in the formula H H H H H H in which R1 is C3H5(OH) it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, if R happened to be C3H5(OH)OC3H5(OH), one could obtain a tetraepoxide. Actually, such procedure generally yields triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterrupted chain. This particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that approxi mately 4 moles of epichlorohydrin yield one mole of the diglycidyl ether, or, stated another way, it can be considered as being formed from one mole of diglycerol and 2 moles of epichlorohydrin so as to give the appropriate diepoxide. The molecular weight is approximately 370 and the number of epoxide groups per molecule are ap proximately 2. For this reason in the first of a series of subsequent examples this particular diglycidyl ether is used, although obviously any of the others previously described would be just as suitable. For convenience, this diepoxide will be referred to as diglycidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethyleneglycol with epichlorohydrin and subsequently with "7 alkali so as to produce a product which, on examination, corresponded approximately to the following compound: H H H H H H H H H H HC-CCCCO-C'COCC-CH H H H H H H The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, is in grams instead of pounds.

Probably the simplest terminology for these polyepoxides, and particularly diepoxides, to differentiate from comparable aryl compounds is to use the terminology epoxyalkanes, and, more particularly, polyepoxyalkanes or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom, and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a he terocyclic ring. The principal class properly may be referred to as polyepoxy polyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetone so as to form the 5-membered ring, followed by conversion of the terminal hydroxyl groups into epoxy radicals.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., It varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms such as a butyl, amyl, hexyl, decyl or dodecyl radical. valent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less. 7

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for in stance, paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such' as benzene, or Xylene, but requires an oxygenated solvent such Where the ditCk as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is'to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368,

dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, low-stage phenolaldehycle resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylol-forming reactivity and are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic hydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

R/ H H H H \R in the reaction product, as indicated in the following As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

R R n R in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For

reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein empioyed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that thebase be neutralized although we have found'that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a f ee base. The amount may be as small as a 200th of a percent and as much as a few lOths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentarner present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I M01. wt Ex- Position R of resin ample R of R derived 'n molecule number from- (based on n+2) Phenyl Para 3. 5 992, 5

Tertiary butyl. 3. 5 882. 5 yl a. 5 882. 5 3. 5 1, 025. 5 3. 5 959. 3. 5 805. 5

3. 5 805. 5 3. 5 1, 036. 5 3. 5 1,190. 5 3. 5 1,267.5 3. 5 1, 344. 5 Dodecyl 3. 5 1, 498. 5 Tertiary butyl. o..." 3. 5 945. 5

Tertiary amyl d 3. 1, 022. 5 Nony do 3. 5 1, 330. 5 Tertiary butyl o 3. 5 1, 071.5

Tertiary arnyl do 3. 5 1, 148. 5 Nonyl d 3. 5 1, 456. 5 Tertiary butyl do 3. 5 1, 008. 5

Tertiary arnyl 3. 5 1,085. 5 Nonyl 3. 5 1, 393. 5 Tertiary butyl 4. 2 996. 6

4. 2 1,083. 4 4. 2 1, 430. 6 Tertiary bu 4. 8 1, 094. 4 Tertiary amyl 4. 8 1,189.6 on 4. s 1, 570. 4 I 1. 5 604. 0 1. 5 646. 0 1. 5 653.0 1. 5 688. 0

2. 0 692. 0 Hexyl 2.0 748.0 Cyclo-hexyl 2. 0 740. 0

-10 PART3 in which R represents a monovalent alkyl, alicyclic, arylalkyl radical which may be heterocyclic in a few instances as in a secondary amine derived from furfurylamine by reaction of ethylene oxide or propylene oxide. Furthermore, at least one of the radicals designed by R must have at least one hydroxyl radical. A large number of secondary amines are available and may be suitably employed as reactants for the present purpose. Among others, one may employ diethanolamine, methyl ethanolamine, dipropanolamine and ethylpropanolamine. Other suitable secondary amines are obtained, of course, by taking any suitable primary amine, such as an alkylamine, an arylalkylamine, or an alicyclic amine, and treating the amine with one mole of an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide. Suitable primary amines which can be so converted into secondary amines, include butylamine, amylamine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine, etc. In other instances secondary amines which have at least one hydroxyl radical can be treated similarly with an oxyalkylating agent, or, for that matter, with an alkylating agent such as benzylchloride, esters of chloroacetic acid, alkyl bromides, dirnethylsulfate esters of sulfonic acid, etc., so as to convert the primary amine into a secondary amine, Among others, such amines include Z-amino-l-butanol, Z-amino-Z-methyl-l-propanol, 2-amino-2-methyl-1,3-propanediol, 2 amino-2-ethyl-1,3- propanediol, and tri(hydroxymethyl) aminomethane. Another example of such amines is illustrated by 4-amino- 4-methyl-2-pentanol.

Similarly, one can prepare suitable secondary amines which have not only a hydroxyl group but also one or more divalent oxygen linkages as part of an ether radical. Examples included are (02 5 (321140 Cz -i) (0 13 70 021140 C2H4O C2H4) HOC2H4 (C-lHaO CHzCH(CHa) 0 (CH3) CECE (CHaO CHzCHzOCHaCHzO CH2CH2) HOCZHA (CHBOCHQGHZCHECHZCHZCH?) /NH HO 02114 or comparable compounds having two hydroxylated groups of difierent lengths as in I (noomomoomomoomom) HOC2H4 Other examples of suitable amines include alpha-methyl 11 benzylamine and monoethanolarnine; also amines obtained by treating cyclohexylmethylamine with one mole of an oxyalkylating agent as previously described; beta-ethylhexyl-butanolamine, diglycerylamine, etc. Another type of amines which is of particular interest because it includes a very definite hydrophile group includes sugar amines such as glucamine, galactamine and fructamine, such as N-hydroxyethylglucamine, N-hydroxyethylgalactamine, and N-hydroxyethylfructamine.

Other suitable amines may be illustrated by CH3 onahcnzon in ontc iornon or the like by reaction with a reagent which contains an epoxide group and a secondary amine group. Such reactants are described, for example, in U. 5. Patents Nos. 1,977,251 and 1,977,253, both dated October 16, 1934, to Stallmann. Among the reactants described in said. letter patent are the following:

PART 4 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by fournula, although it may be so illustrated in an idealized simplification, it is difiicult to actually depict the final product of the cogeneric mixture except in terms of the process itself. I

- A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. in most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for Thus, we have.

instance, ordinary room temperature. found it convenient to use a solvent and particularly one which can be removed readily at a comparatively mode-rlate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar sol vents. Indeed, resins which are mot soluble except in oxygenated solvents or mixtures containing such solvents are not here included [as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be'used or one can use a comparatively non-volatile solvent such as :dioxane or the diethyl-ether of ethyleneglycol. One can also use 'a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is em ployed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difiicult perhaps to ladd a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected tosome further reaction where the solvent may be objectionable as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohols should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an 7 advantage for reasons stated.

The products obtained, depending on the reactants selected, may be water-insoluble, or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc.

We have found no particular advantage in using a low temperature in the early stage of the reaction. because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a gen- :eral way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed [as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may beanything from a few hours'up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for form aldehyde to be lost. Thus, if the reaction can be conducted latwa lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue heat convertibility as previously referred to. i

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or out but may be convenient under certain circumstances.

On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the 'reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely dissolved. However if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the amine is added and stirred. Depending on the amine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example, 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to usea commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C., for 4 or 5 hours, or at the most, up to -24 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of amine or formaldehyde. At a higher temperature we use a phaseseparating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C., and below 150 C., by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary amine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in-the usual ways, including the amount of water of reaction, molecular weight and particularly in some instances have checked whether or not the end product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted amine, if any is present, is another index.

in light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the'herein described condensation products. The following example will serve by way of illustration.

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding were powdered and mixed with 700 grams of xylene. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C. and

210 grams of diethanolamine added. The mixture was.

stirred vigorously and formaldehyde added slowly. The formaldehyde used was a 37% solution and 160 grams were employed which were added in about 3 hours. The mixture wasstirred vigorously and kept within a temperature range of 30 to 45 C. for about 21 hours. At the end of this period of time it was refluxed, using a phase-separating trap anda small amount of aqueous distillate withdrawn from time to time and the presence of unreacted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within approximately 3 hours after the refluxing was started. As soon as the odor of formaldehyde was no longer detectible the phaseseparating trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached about 150 C. The mass was kept at this higher temperature for about 3% hours and reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or a tacky resin. The overall reaction time was a little over 30 hours. In other instances it has varied from approximately 24 to 36 hours. The time can be reduced by cutting the low temperature period to about 3 to 6 hours.

Note that in Table I1 following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of to C. or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

TABLE H Strength of Reac- Reac- Max Ex. Resin Amt., formal- Solvent used tion tion dis- No. used grs. Amine used and amount dehyde and amt. temp., time till.

soln. and 0. (hrs) temp.,

amt. C.

882 Diethanolamine, 210 g 37%, 162 g. Xylene, 700 g 22-26 32 137 480 Diethanolamine, 105 g 37%, 81 g Xylene, 450 g. 21-23 28 150 633 .t do .do Xylene. 600 g 20-22 36 145 441 Dipropanolamine, 133 g 30%, 100 g Xylene, 400 gm. 20-23 34 146 480 (lo d Xylene, 450 g 21-23 24 141 633 do ..d0 Xylene, 600 g. 21-28 24 145 882 Ethylethanolamine, 178 g 37%, 162 g... Xylene, 700 g 20-26 24 152 480 Ethylethanolamhle, 89 g. 81 g Xylene, 450 g 24-30 28 151 633 do do Xylene, 600 g 22-25 27 147 473 Cyclohexylethanolamine, 143 g v. 30%, 100 g Xylene, 450 g 21-31 31 146 511 do 37%, 81 g .d0 22-23 36 148 665 do d Xylene, 550 g... 20-24 27 152 C2H5OCZH4OCZH4 1317---. 2a 441 NH, 176 g .d0 Xylene, 400 g 21-25 24 150 C2H5OCZH4OCZH4 14b a"-.. 480 NH, 176 g -d0 Xylene, 450 g 20-26 26 146 CZH5OCZH4OOZH4 15b 9a-.." 595 NH, 176 g d0 Xylene, 550 g. 21-27 30 147 HOC2H4 HOC2H4OC2H4OC2H4 16b 2u-. 441 NH, 192 g -d0 Xylene, 400 g.-- -22 30 148 HOO2H4OC2H4O 01H;

17]). 5|z 480 NH, 192 g. ..do. do 20-25 28 150 HOO H;

HOCzH4OCzH4OC2 4 18b 14a 511 NH, 192 g do Xylene, 500 g.... 21-24 32 149 HOC2H4 HOC2H4OCzH4OC2H4 19b 22a 4998 NH, 192 gm -do Xylene, 450 g-. 22-25 32 153 HOC2H4 CH3(OC:H4)3

2011--.. 2311.-.. 542 NH, 206 g 30%, 100 gm Xylene, 500 g 21-23 36 151 nocini OH (OO:H4)3

21ba 547 NH, 206 g .;..do .-do 25-30 34 148 HOCQH CH:(OC2H4)3 22b 2a 441 NH, 206 g (10 Xylene, 400 g.... 22-23 31 146 23h. 2611.". 595 Decylethanolamine, 201 g 37%, 81 g. Xylene, 500 g 22-27 24 145 24b 27a 391 Decylethanolamine, 100 g 30%, gm. Xylene, 300 g 21-25 26 1 47 PART 5 1b. Condensate lb was in turn obtained from diethanol- Th6 preparation of ,oxyalkylated derivatives of Prod; amine and the resin previously identified as Example 2a.

nets of the kind which appear as examples in Part 4 is carried out by procedures and in apparatus which are substantially conventional for oxyalkylation, and which will be illustrated by the following examples. In preparing the products of the examples, a conventional autoclave with required accessories for oxyalkylation having a capacity of about 25 gallons is used.

I Example 10 t v The oxyalkylation-susceptible compound employed is Reference to Table I shows that this particular resin is obtained from para-tertiarybutylphenol and formaldehyde. 11.16 pounds of this resin condensate were dissolved in 7 pounds of solvent (xylene) along with one ponndrof finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately C. to C., and at a pressure of about 15 to 20 pounds.

The time regulator Was set so as to inject the ethylene oxide in approximately two hours and then continue the one previously described and designated as Example stirring for a half-hour or longer. The reaction went eat-am readily and, as a matter of fact, the oxide was taken up almost immediately. Indeed the reaction was complete in less than an hour. More specifically it was complete in 45 minutes. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 11.16 pounds. This represented a molal ratio of 25 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 2232. A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables III and IV.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example 20 This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example 1b, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example to wit, 11.16 pounds. The amount of oxide present in the initial step was 11.16 pounds, the amount of catalyst remained the same, to wit, one pound, and the amount of solvent remained the same. The amount of oxide added was another 11.16 pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 22.32 pounds and the molal ratio of ethylene oxide to resin condensate was 50.8 to 1. The theoretical molecular Weight was 3348.

The maximum temperature during the operation was 130 C. to 135 C. The maximum pressure was in the range of to pounds. The time period was one hour.

Example 30 The oxyalkylation proceeded in the same manner described in Examples 10 and 2c. There was no added solvent and no added catalyst. The oxide added was 11.16 pounds and the total oxide at the end of the oxyethylation step was 33.48 pounds. The molal ratio of oxide to condensate was 76.2 to 1. Conditions as far as temperature and pressure and time were concerned were all the same as in Examples 10 and 2c. The time period was somewhat longer than in previous examples, to wit, 2 hours.

Example 40 The oxyethylation was continued and the amount of oxide added again was 11.16 pounds. There was no added catalyst and no added solvent. The theoretical molecular weight at the end of the reaction period was 5580. The molal ratio of oxide to condensate was 101.6 to 1. Conditions as far as temperature and pressure were concerned were the same as in previous examples. The time V 18 V period was slightly longer, to wit, 3 /2 hours. The reaction unquestionably began to slow up somewhat.

Example 50 The oxyethylation continued with the introduction of another 11.16 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added. The theoretical molecular weight at the end of the agitation period was 6696, and the molal ratio of oxide to resin condensate was 127 to 1. The time period, however, dropped to 1% hours. Operating temperature and pressure remained the same as in the previous example.

Example 6c The same procedure was followed as in the previous examples except that an added pound of powdered caustic soda was introduced to speed up the reaction. The amount of oxide added was another 11.16 pounds, bringing the total oxide introduced to 66.96 pounds. The temperature and pressure during this period were the same as before. There was no added catalyst and also no added solvent. The time period was 2 /2 hours.

Example 7c The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 78.12 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 8928. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 3 hours.

Example 8c This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 89.28 pounds. The theoretical molecular weight was 10,044. The molal ratio of oxide to resin condensate was 203.2 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 4 hours.

The same procedure as described in the previous examples are employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 10 through 400 were obtained by the use of ethylene oxide, whereas 41c through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows.

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible compound, to wit, the resin condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide alone is employed; as happens to be the ease in Example through 40c, the amount of oxide present in the oxyalkylation derivatives is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The th column shows the theoretical molecular weight at the end of the oxyalkylation period.

Tl'1e8th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column '8 coincides with the figure in column 3. 7

Column 9 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 10 can be ignored insofar that no propylene oxide was employed.

Column 11 shows the catalyst at the end of the reaction period.

Column 12 shows the amount of solvent at the end of the reaction period.

Column 13 shows the molal ratio of ethylene oxide to condensate.

Column 14 can be ignored for the reason that no pro ylene oxide was employed.

Referring now to Table Vi. It is to be noted that the first column refers to Examples 10, 20, 3c, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present. with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV, Examples 41c through 80c are the counterparts of Examples 10 through 40c, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, two columns are blank, to wit, columns 4 and 9.

Reference is now made to Table V. It is to be noted these compoundsare designated by d numbers, 1d, 2d, 3d, etc., through and including 32d. They are derived, in turn, from compounds in the a series, for example, 350, 39c, 53c and 620. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds 1c through 401: were obtained by the use of ethylene oxide, it is obvious that those obtained from 35c and 390, involve the use of ethylene oxide first, and propylene oxide afterward. Inversely, those compounds obtained from 530 and 62c obviously came from a prior series in which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as 1d, 2d, 3d, etc., the initial 0 series such as 350, 39c, 53c, and 626, were duplicated and' the oxyalkylation stopped at the point designated instead of being carried further as may have been the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in' 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 1d, it will be noted that the initial product, i. e., 350, consisted of the reaction product involving 11.16 pounds of the resin condensate, 16.74 pounds of ethylene oxide, 1.0 pound of caustic soda, an-d 7.0 pounds of the solvent.

It is .to be noted that reference to the catalyst in Table V refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total solventpresent, i. e., that from the first oxyalkylation step plus added solvent, if any.

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylation step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of the next step, except obviously at the very start the value depends on the theoretical molecular weight at the end of the initial oxyalkylation step; i. e., oxyethylation for 1d through 16d, and oxypropylation for 17d through 32d.

It will be noted also that under the molal ratio the values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions is substantially the sameas before and appears 'in Table VI.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation and particularly vacuum distillation. Such distillation also may remove'traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indiiferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then-g0 back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use adarker colored aromatic petroleum solvent. oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen atom, the removal of the alkaline catalyst is somewhat more difficult than ordinarily is the case for the'reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present. i

TABLE V Composition before Composition at end Molal ratlo Molec. Ex. N o. wt.

-8 OS" Ethl. Propl. Oata- Sol- O-S* Ethl. Prop]. Oata- Sol- Ethyl. Propl. based cmpd., cmp l., oxide, oxide, lyst, vent, cmpd., oxide, oxide, lyst, vent, oxide oxide on theex. No. s. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. lbs. to oxyto oxyoretical alkyl. alkyl. value suscept. suscept. cmpd. cmpd.

'Oxyalkylation-susceptlble.

TABLE VI Max. Max. Solubility Ex. temp., pres., Time, No. C. p. s.1. hrs.

Water Xylene Kerosene 15-20 Insoluble 1520 1 Emulsifiable. 15-20 2 solufleu Insoluble. Disperslble. Soluble.

Illlllil)llllllll'lllll lll TABLE vr-oouum ee Max. Max. Solubility Ex. temp, pres, Time, No. C. p. s. 1. hrs.

Water Xylene Kerosene 51c 125-130 25-85 2 Insoluble Soluble Dlsperslble. 520.. 125-130 25-35 3 d d Soluble. 530.- 125-130 25-35 D0. 540.. 125-130 25-35 Do. 652.- 125-130 25-35 D0. 566.. 125-130 25-35 D0. 570 130-135 5-10 Insoluble. 586.- 130-135 5-10 Disperslble. 590.. 130-135 5-10 D0. 600. 130-135 5-10 Soluble 61c. 130-135 5-10 Do. 620. 130-135 5-10 D0. 630. 130-135 5-10 D0. 640. 130-135 5-10 Do. 650. 125-135 -20 Insoluble. 66c. 125-135 15-20 D0. 67c. 125-135 15-20 Dispersible. 68c- 125-135 15-20 Soluble. 69c. 125-135 15-20 Do. 700. 125-135 15-20 D0. 710. 125-135 15-20 D0. 72c. 125-135 15-20 D0. 73c.. 125-130 15-20 Insoluble 740.. 125-130 15-20 Do.

125-130 15-20 D0. 125-130 15-20 Dlspersible. 12.5-130 15-20 Soluble. 125-130 15-20 D0. 125-130 15-20 D0. 125-130 15-20 Do. 125-130 15-20 Insoluble 125- 130 15-20 D0. 125-130 15-20 D0. 125-130 15-20 D0. 125-130 15-20 Do. 125-130 15-20 Do. 125-130 15-20 Dispersible. 125-130 15-20 uble. 125-130 15-20 Insoluble. 125-130 15-20 D0. 125-130 15-20 D0. 125-130 15-20 D0. 125-130 15-20 Do. 125-130 15-20 Do. 125-130 15-20 Disperslble. 125-130 15-20 Soluble. 125-130 -30 DO. 125-130 25-30 D0. 125-130 25-30 D0. 125-130 25-30 Dlsperslble. 125-130 25-30 Insoluble. 125-130 25-30 -.-.Do. 125-130 25-30 D0. 125-130 25-30 D0. 130-135 5-10 Soluble. 130-135 5-10 D0. 130-135 5-10 D0. 130-135 5-10 D0. 130-135 5-10 Dtspersible. d 130-135 5-10 Insoluble. d 130-135 5-10 D0. 32d 130-135 5-10 D0.

PART 6 clay or speclally prepared mineral catalysts have been The resin condensates which are employed as intermediate reactants are strongly basic. Initial oxyalkylation of these products with a monoepoxide or diepoxide can be accomplished generally, at least in the initial stage, Without the addition of the usual alkaline catalyst such as those described in connection with oxyalkylation employing monoepoxides in Part 5 immediately preceding. As a matter of fact, the procedure is substantially the same as using a non-volatile monoepoxide such as glycide or methylglycide. However, during progressive oxyalkylation with a monoepoxide it is usually necessary to use a catalyst as previously described and, thus, there may or may not be suficient catalyst present for the reaction with the diepoxide. Reference to the catalyst present includes the residual catalyst remaining from the oxyalkylation step in which the monoepoxide was used.

Briefly stated then, employing polyepoxides in combination with a non-basic reactant the usual catalysts in clude alkaline materials, such as caustic soda, caustic potash, sodium methylate, etc. acidic in nature and are of the kind illustrated by iron and tin chloride, Furthermore, insoluble catalystssuch as ()ther catalysts may beused. If for any reason the reaction does not proceed rapidly enough with the diglycidyl ether or other analogous reactant then a small amount of finely divided caustic soda or sodium methylate can be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes Without saying that the reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethyleneglycol, or the diethylether of propyleneglycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solvent-free and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, then xylene or an aromatic petroleum solvent will serve. If the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not 75 ya y o -suscept b et i ea y en h to select a .21! suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the most economical one.

Example of condensate 1b was described in Part 4, preceding. 10

Details have been included in regard to both steps. Con densate 1b, in turn, was obtained from diethanolamine and resin 2a; resin 2a, in turn was obtained from paratertiarybutylphenol and formaldehyde.

In any event, 223 grams of the oxyalkylated resin con- 15.

densate previously identified as 10 were dissolved in a proximately an equal weight of xylene. About 2.25 grams of sodium methylate were added as a catalyst so the total amount of catalyst present, including residual catalyst from the prior oxyalkylation, was about 2.4 grams. 18.5

grams of diepoxide A were mixed with an equal weight of xylene. The initial addition of the diepoxide solution was. made after raising the temperature of the reaction mass to about 105 C. The diepoxide was added slowly over a period of about one hour. temperature was allowed to rise to about 125 C. The mixture was allowed to reflux at about 135140 C. using a phase-separating trap. A small amount of xylene was removed by means of a phase-separating trap so the liq i plate in order to examine the physical properties. The material was an amber, or light reddish amber, viscous It 'Was insoluble in water; it was insoluble in gluconic acid, but it was soluble in xylene and particularly in a mixture of 80% xylene and 20% methanol. However, if the material Was dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed" a definite tendency to disperse, suspend, or form a sol, and particularlyin a xylene-methanol mixed solvent as previously described, with or without the further addition of a little acetone. 7 Generally speaking, the solubility of these derivatives is in line with expectations by merely examining the solu-' bility of the preceding intermediates, to wit, the oxyalkylated resin condensates prior to treatment with the diepoxide. These materials, of course, vary from extremely water-soluble products due to substantial oxyethylation, to those which conversely are Water-insoluble but xylene-soluble or even kerosene-soluble due to high stage oxypropylation. Reactions with diepoxides or polyepoxides' of the kind herein described reduce the hydrophile properties and increase the hydrophobe properties, i. e., generally make the products more soluble in kerosene or a mixture of kerosene and xylene, or in xylene,

During this time the but less soluble in water. Since this is a general rule which applies throughout, for sake of brevity future reference to 7 solubility will be omitted.

The procedure employed, of course, is simple in light; of what has been said previously and in effect is a prorefluxing temperature rose gradually to about 155 C. 30 ceduresimilar to that employed in the use of glycide or The mixture was refluxed at this temperature for about 3 /2 hours. At the end of this period the xylene which had been removed by means of the phase-separating trap was returned to the mixture. A small amount of 'material was withdrawn and the xylene evaporated on a hot methylglycide as oxyalkylating agents. See, for example,

f Part 1 of U. S. Patent No. 2,602,062 dated July 1, 1952,

to De Croote.

Various examples obtained in substantially the same 'manner are enumerated in the following tables:

TABLE VII Ex. Qxy. Amt., Diep- Amt., Catalyst iXy- Molar Time 01' Max. No. resin congrs. oxide grs. (N aOCHa), 'lene, ratio reaction, temp., Color and physical state densate used grs. grs. hrs. C.

223 A 18. 5 2. 4 242 2:1 3. 5 155 Reddish amber resinous mass. 375 A 18.5 3. 9 394 2:1 3. 5 152 D0. 271 A 9. 3 2.8 '280 2: 1 3. 5 148 D0 377 A 9. 3 3. 9 '386 2:1 3. 5 150 D0 113 A 1.9 1.1 2:1 3.4 160 D0 335 A 18. 5 3. 5 354 2:1 3 154 Do 375 A 18. 5 3. 9 '394 2:1 4 155 D0 271 A 9. 3 2. 8 280 2:1 4 165 D0. 314 A 9. 3 3. 2 323 2:1 4 D0. 363 A 9. 3 3. 7 372 2:1 4 165 D0. 391 A 18. 5 4. 1 409 2:1 4 160 D0. 279 A 9. 3 2. 9 288 2: 1 4 164 D0 363 A 9. 3 3. 7 372 2:1 4 Do 100 A 1. 9 1.0 102 2: 1 3. 5 D0 152 A 1. 9 1. 5 154 2:1 4 165 Do TABLE VIII Ex. Oxy. Amt., Diep- Amt, Catalyst Xy- Molar Time of Max. No. resin congrs. oxide grs. (N EOCHQ), lene, ratio reaction, temp., Color and physical state densate used g-rs. grs. hrs. C.

223 B 11 2. 3 234 2:1 4 Reddish amber resinous mass. 375 B 11 3. 9 386 2:1 4 155 D0. 271 B 5. 5 2.8 277 2:1 4 152 Do. 377 B 5. 6 3. 8 383 2:1 4 154 Do. 113 B 1. 1 1. 1 114 2:1 3. 5 154 Do. 335 B 11 3. 5 346 2: 1 4 150 D0. 375 B 11 3. 9 386 2:1 4 Do. 271 B 5. 5 2. 8 277 2:1 4 158 Do 314 B 5. 5 3. 2 320 2:1 4. 5 152 D0 363 B 5. 5 3. 7 369 2: 1 4. 5 160 Do. 391 B 11 4.0 402 2:1 4 158 D0. 279 B. 5. 5 2. 9 285 2:1 4 153 Do. 363 B 5. 5 3. 7 369 2:1 4 155 Do. 100 B 1. 1 1. 0 101 2:1 3 155 Do. 152 B 1.1 1. 5 153 2:1 4 V 158 Do.

swa ger TABLE IX Prob. mol. Ex. No. Oxyalkyl. weight of Amount of Amount of resin conreaction product, grs. solvent densate product TABLE X Prob. mol. Ex. No. Oxyalkyl. weight of Amount of Amount of resin conreaction product, grs. solvent densate product At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as Xylene or the like. In some instances an oxygenated solvent, such as the diethylether or ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperaure of reaction by adding a small amount of initially lower boiling solvent, such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance, 90% to 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular Weight dimensions on either the resin molecule or the diepoxide molecule actually may vary from the true molecular weight by several percent.

The condensate can be depicted in a simplified form which, for convenience, may be shown thus:

(Amine)CH2(Resin) CH2(A1nine) Following such simplification the reaction with a polyepoxide, and particularly a diepoxide, would be depicted thus:

(Amine)OH;(Oxyalkylt1ted Resin)CH2(Amine) I (Amlne)CHz(0xyalky1ated Resin)CH2(Amino) in which D. G. E. represents a diglycidyl ether as specified.

3Q As has been pointed out previously, the condensation reaction may produce other products, including, for ex ample, a product which may be indicated thus in light of what has been said previously:

[ (Amine) CH2 (Resin) 1 This product, since it is susceptible to oxyalkylation by means of the oxyalkylated phenolic hydroxyl groups and depending on the selection of the amine, may be susceptible to oxyalkylation in event a hydroxylated amine or polyamine had been used, and may be indicated in the following manner:

[Oxyalkylated(Amine) CH2(Resin) 1 When a diglycidyl other is employed one would obviously obtain compounds which two molecules of the kind described immediately preceding are united in a manner comparable to that previously described, which may be indicated thus:

Likewise, it is obvious that the two different types of oxyalkylation-susceptible compounds may combine so as to give molecules which may be indicated thus:

gnminemflzwxyalhylated Resinmliflmnincl) til W1 Oxyalkylated (Amino) CH (Resin) Oxyalkylated (Amine) CHAAmiue) m-n m-u-n-a-I Oxyollrylated(Amine)OHg(Resin) Oxyalkylated (Amine) CHflAmine) L j PART 7 As to the use of conventional deinulsifying agents reference is made to U. S. Patent No. 2,626,929, dated January 7, 1943, to De Grootc, and particularly to Part Three. Everything that appears therein applies with equal force and effect'to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 3e, herein described.

Having thus described our invention what we claim as new and desireto secure by Letters Patent is: Y

1. A process for breaking petroleum emulsions of the water-inoil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being obtained by a three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide; said first manufacturing step being a method of (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, Water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and then completing the reaction by a third step of (C) reacting said oxyalkylated resin condensate with nonaryl hydrophile polyepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical H H H -%o -/0H in the polyepoxide, is water-soluble, said polyepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; with the further proviso that said reactive monoepoxide-derived compounds (AA) and nonaryl polyepoxides (BB) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; said reaction between (AA) and (BB) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reacants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl polyepoxide.

2. A process for breaking petroleum emulsions of the Water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being obtained by a three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a polyepoxide; said first manufacturing step being a method of (A) condensing (a) an oxyalkylanon-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight com:-

spending to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in reand reactive toward said phenol; said ,,resin being.

formed in the substantial absence of trifunctional phenols; said phenol being of the formula s in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated;

secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and then completing the reaction by a third step of (C) reacting said oxyalkylated resin condensate with nonarylhydrophile polyepoxides characterized by I the fact that the precursory polyhydric alcohol, in which an oxygen-linked hydrogen atom is replaced subsequently by the radical in the polyepoxide, is water-soluble; said polyepoxides being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said polyepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive monoepoxide-derived compounds (AA) and nonaryl polyepoxides (BB) be members of the class consisting of non-thermosetting organic solvent-soluble'liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of solvents soluble liquids and low-melting solids; said reaction between (AA) and (BB) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl polyepoxide.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being obtained by a three-step manufacturing process involv ing (1)c0ndensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a diepoxide; said first manufacturing step being a method of (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula I in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkyladon-susceptible; followed as a second step by (B) oxyalkylation by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and then completing the reaction by a third step of (C) reacting said oxyalkylated resin condensate with nonaryl hydrophile diepoxides characterized by the fact that the precursory polyhydric alcohol, in which an oxygenlinked hydrogen atom is replaced subsequently by the radical in the diepoxide, is water-soluble; said diepoxide being free from reactive functional groups other than epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said diepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive monoepoxide-derived compounds (AA) and nonaryl diepoxides (BB) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of solventsoluble liquids and low-melting solids; said reaction between (AA) and (BB) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the nonaryl diepoxide.

4. The process of claim 3 wherein the diepoxide contains at least one reactive hydroxyl radical.

5. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier; said demulsifier being obtained by a three-step manufacturing process involving (1) condensation; (2) oxyalkylation with a monoepoxide; and (3) oxyalkylation with a diepoxide; said first manufacturing step being a method of (A) condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed as a second step by (B) oxyalkylation by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methyl-glycide; and then completing the reaction by a third step of (C) reacting said oxyalkylated resin condensate with a hydroxylated diepoxypolyglycerol having not more than 20 carbon atoms; with the further proviso that said monoepoxide-derived compounds (AA) and said hydroxylated diepoxyglycerol (BB) be members of the class consisting of non-thermosetting organic solventsoluble liquids and low-melting solids; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and low-melting solids; said reaction between (AA) and (BB) be conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the oxyalkylated resin condensate to 1 mole of the hydroxylated diepoxyglycerol.

6. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei.

7. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the percursory phenol is para-substituted.

8. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substitutde and contains at least 4 and not over 14 carbon atoms in the substituent group.

9. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the precursory aldehyde is formaldehyde.

10. The process of claim 5 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the precursory aldehyde is formaldehyde, and the total number of phenolic nuclei in the initial resin is not over 5.

11. The process of claim 1 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

12. The process of claim 2 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

13. The process of claim 3 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is (b) the free base, and (c) the salt of gluconic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water. I

14. The process o"c1aimt.4: withztheaprnviso tliattheb hydrophile properties of the product of. the: condensation" reactionemployed. insthet form Ufl'a' member: of thetclass consisting of (a the anhydro base as is (.12?) the free base, and' (a) the salt ofrgluc'onicaacid, inan equaliweight. 5-; of Xylene are sutficient to: produce an emulsion when. said-xylene solution; is. shaken vigorously with: l; to 3 volumes of water;

15. The-process of claim 5 with the. proviso thattthe hydrophile properties of the product of the condensation- 10' reactionemployed in: the form; of a'- member of the class consisting ofv (a) the anhydro' baseas is, (h): the: free base; and? (c) the'sa'lt of. gluco'nic acidg in anaequaltwei ght ofv xylene are. sufficient to: produce an ernulsiont when said xylene solution is shaken vigorously with 1 to 3 15' volumes: of: waters.

16'.- The process of claim.6 with: the proviso that the" hydrophile properties of. therprodu'ct of. the condensation reaetiom employeds ini'th'e' form of? a: member off the: class? consisting: of (a) the: anhydr'o' base as-is; (b the free 2o base, a'nd" (c') the salt of gluconic'a'cid inansequal weight of: xylene are: sufiicient to produce-amemulsio'm when: said: xylene'solutioniis shaken vigorouslywith l toi3=vo1umes of water;

17;. The process: of: claim. 7 with the: proviso that the 25-.

hydrophile properties of the product of tlle condensae' tion: reactionl employed in the form of a member. of. the class consisting. of (a). the anhydro' base asis" (b)i the free base, and (c) the' salt of) gluconic acid", in; any

equal weight of xylene are sufiicient toi produce ante'muh 3'0 sion when said xylene solution is: shakenazvigorously with 1 to 3 volumes of water. a

a 18. The process of'claim 8 with the proviso that the 6 6 hydrophilet properties of: the product of the condensation reaction employed in the form of a member of the class 19. The process of claim 9 with the proviso. that the hydrophile properties of the product of the condensation reaction employed in the form of'amernber of. the class consisting of (a) the anhydro base as is, (b') the free base, and (c). the salt of glucouic acid, in an equal. weight of Xylene are sufiicient; to produce an emulsion,

when said xylene solution is shaken vigorously with 1 m3 volumes of water.

20. The process of claim 10 with therproviso that thehydrophile properties of the product ofthecondensa-- tion reaction employed in the form. of amernber: of; the

class'consistings of (a) the anhydro base' asis (Ix-)thefree base, and (c) the salt of. gluconic acid,inlan equal weight of Xylene are suificient to produce an: emulsion when saidfxylene; solution is shaken vigorously with. 1 to 3 volumes ofwater.

References Cited in the file of this patent UNITED STATES PATENTS 2,395,739 Hersberger Feb. 26, 1946 2,454,541 Bock et a1. Nov. 23, 1948 2,457,634 Bond et al. Dec. 28, 1948 2,589,198 Monson Mar. 11, 1952 2,695,888 De Groote Nov. 30, 1954 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER; SAID DEMULSIFIER BEING OBTAINED BY A THREE-STEP MANUFACTURING PROCESS INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A MONOEPOXIDE; AND (3) OXYALKYLATION WITH A POLYEPOXIDE; SAID FIRST MANUFACTURING STEP BEING A METHOD OF (A) CONDENSING (A) AN OXYALKLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOLALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 